methyl (1S,3S,5R)-5-acetyloxy-1,3-dichloro-3-formyl-2,2-dimethoxycyclopentane-1-carboxylate | 894793-48-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl (1S,3S,5R)-5-acetyloxy-1,3-dichloro-3-formyl-2,2-dimethoxycyclopentane-1-carboxylate
• CAS: 894793-48-7
• 化学式: C₁₂H₁₆Cl₂O₇
• 分子量: 343.161
• InChiKey: WYXCYVMAWMMCMW-DVVUODLYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  88.1
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  methyl (1S,3S,5R)-5-acetyloxy-1,3-dichloro-3-formyl-2,2-dimethoxycyclopentane-1-carboxylate 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 反应 8.0h， 以89%的产率得到
  参考文献：
  名称：

  Unexpected formation of a chiral δ-lactone by reduction of the 1,3-dicarbonylic cyclopentanoid derivatives

  摘要：

  We have described the synthesis of highly functionalized chiral cyclopentanoids, which are important building units for synthesis of biological active compounds. The (-)- or (+)-7,7-dimethoxy-1,4,5,6-tetrachlorobicyclo[2.2.1]hept-5-en-2-endo-yl acetate, obtained from the enzyme catalyzed transesterification of the racemate, was converted to alpha-diketone chiral. The alpha-diketone was treated with H2O2/NaOH and esterified with CH2N2 to furnish a mixture of the compounds (+)- or (-)-10 and (+)- or (-)-11. The reduction of the (+)- or (-)-10 and/or (+)- or (-)-11 with BH3 center dot THF furnished the lactone (+)- or (-)-13 with excellent yield. The alpha-diketone was reduced with indium metal in the presence of NH4Cl furnishing the acyloin (+)-14 in 67%, of yield. The treatment of acyloin (+)-14 with Pb(OAc)(4) furnished the aldehyde (+)-15 with 80% of yield. The reduction of the aldehyde (+)-15 with NaBH4 has again produced the lactone (+)-13. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2006.03.062
• 作为产物：
  描述：

  (1RS,2SR,4SR)-7,7-dimethoxy-1,4,5,6-tetrachlorobicyclo<2.2.1>hept-5-en-2-ol 在 lead(IV) acetate 、 4-二甲氨基吡啶 、 ruthenium trichloride 、 indium 、 sodium periodate 、 氯化铵 作用下， 以 甲醇 、 乙腈 、 苯 为溶剂， 反应 27.67h， 生成 methyl (1S,3S,5R)-5-acetyloxy-1,3-dichloro-3-formyl-2,2-dimethoxycyclopentane-1-carboxylate
  参考文献：
  名称：

  Unexpected formation of a chiral δ-lactone by reduction of the 1,3-dicarbonylic cyclopentanoid derivatives

  摘要：

  We have described the synthesis of highly functionalized chiral cyclopentanoids, which are important building units for synthesis of biological active compounds. The (-)- or (+)-7,7-dimethoxy-1,4,5,6-tetrachlorobicyclo[2.2.1]hept-5-en-2-endo-yl acetate, obtained from the enzyme catalyzed transesterification of the racemate, was converted to alpha-diketone chiral. The alpha-diketone was treated with H2O2/NaOH and esterified with CH2N2 to furnish a mixture of the compounds (+)- or (-)-10 and (+)- or (-)-11. The reduction of the (+)- or (-)-10 and/or (+)- or (-)-11 with BH3 center dot THF furnished the lactone (+)- or (-)-13 with excellent yield. The alpha-diketone was reduced with indium metal in the presence of NH4Cl furnishing the acyloin (+)-14 in 67%, of yield. The treatment of acyloin (+)-14 with Pb(OAc)(4) furnished the aldehyde (+)-15 with 80% of yield. The reduction of the aldehyde (+)-15 with NaBH4 has again produced the lactone (+)-13. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2006.03.062

文献信息

• Indium-Mediated Regio- and Diastereoselective Reduction of Norbornylα-Diketones
  作者：Faiz Ahmed Khan、Jyotirmayee Dash、Ch. Sudheer

  DOI：10.1002/chem.200305656

  日期：2004.5.17

  bicyclic alpha-diketones into synthetically useful acyloins mediated by indium metal is described. The reduction is highly diastereoselective, leading exclusively to endo-acyloins (endo-hydroxyl groups) in excellent yields, and tolerates a variety of sensitive substituents, such as acetate, ester, and bridgehead halogens. The regioselectivity in the reductions of monosubstituted alpha-diketones varied

  描述了一种新的，有效的，区域性的以及非对映选择性的将非可烯化的双环α-二酮转化为铟金属介导的合成有用的酰基辅酶的方法。该还原是高度非对映选择性的，仅以优异的产率仅产生内酰基-糖苷（内羟基），并耐受各种敏感的取代基，例如乙酸盐，酯和桥头卤素。对于两种可能的异构醇，在单取代的α-二酮还原中的区域选择性从70:30到100：0不等。该方法扩展到了高度官能化的环戊烷甲醛的合成，这是有机合成中的潜在组成部分，通过在MeOH / PhH中用Pb（OAc）4处理酰基转移酶来裂解酰基转移酶。